JPH05247143A - Preparation of monoethylenically unsaturated dicarboxylic acid homopolymer and copolymer and detergent additive and tableware detergent additive composed thereof - Google Patents

Abstract

PURPOSE: To obtain a monoethylenically unsaturated carboxylic acid copolymer having a small amount of residual unsaturated carboxylic acid by polymerizing a 4-8C monoethylenically unsaturated dicarboxylic acid, a hydroxy 2-4C alkyl acrylate, etc., and other monomers, etc., under specific conditions.

CONSTITUTION: (A) a 4-8C monoethylenically unsaturated dicarboxylic acid, (B) a hydroxy 2-4C alkyl acrylate and/or a hydroxy 2-4C alkyl methacylate and (C) other water soluble monoethylenically unsaturated monomers are mixed in such a manner that the (weight) ratio of component (A): component (B): component (C) comes to (100-65):(0-35):(0-35) and radically polymerized in an aqueous solution in a partially neutralized form with a neutralization ratio of 52-70% to obtain the desired copolymer having a Kvalue of 7-50. For example, in preparing a copolymer from components (A) and (C), components (A) and (C) are used at a (weight) ratio of component (A) to component (C) of (99-65):(1-35) and first, component (A) is neutralized to a neutralization ratio of 85% with an alkali metal, ammonia or an amine and then, an polymerization initiator is added in accordance with the progression of polymerization of component (C) having an acid group in an unneutralized form to conduct the polymerization.

COPYRIGHT: (C)1993,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing homopolymers and copolymers of monoethylenically unsaturated dicarboxylic acids and detergent and dishwashing detergent additives containing the same.

[0002]

2. Description of the Prior Art From EP-A-0075820, a monoethylenically unsaturated dicarboxylic acid, for example 10 to 60% by weight of maleic acid, and a monoethylenically unsaturated monocarboxylic acid having 3 to 10 C atoms are disclosed. An acid, for example 90-40% by weight of acrylic acid, at a neutralization rate of 20-80% during the polymerization reaction in an aqueous medium at 60-150 ° C.
It is known to prepare copolymers of monoethylenically unsaturated monocarboxylic acids and dicarboxylic acids which are polymerized in an aqueous medium at 0.5 ° C. with 0.5 to 5% by weight of water-soluble initiator for the monomers. According to this method, a copolymer having a residual amount of unpolymerized dicarboxylic acid of less than 1.5% by weight is obtained.

German Patent Application Publication No. 3512
From H.223, maleic acid homopolymers and copolymers can be obtained by copolymerizing maleic acid in an aqueous medium, optionally with other water-soluble ethylenically unsaturated monomers, in the presence of a polymerization initiator. Manufacturing is known. In this method, maleic acid is first neutralized with an alkali metal hydroxide or ammonia to a molar ratio of 100: 0 to 100: 90, and then polymerized by adding a polymerization initiator. During the progress of the polymerization, an alkali metal hydroxide or ammonia was further added, and the molar ratio of maleic acid to base was 100: 100 to 100: 130.
To the reaction mixture. The polymerization is then completed. However, according to these examples, the ratio of maleic acid to caustic soda liquor is less than 1: 1 after the end of the polymerization. The polymers that can be produced in this way have a narrow molecular weight distribution and 200-2000.
It has a molecular weight in the range of 0. According to the description of this specification, a high polymerization rate cannot be achieved outside the above-mentioned neutralization range for maleic acid. The copolymers are used, for example, as scale inhibitors in boilers or demineralizers, as detergent builders and as dispersants for inorganic pigments.

EP-A-0337694 discloses that maleic acid is present in aqueous media at 0.5-500 ppm, optionally together with 50-0.1% by weight of other water-soluble ethylenically unsaturated monomers. 300-50 by polymerizing in the presence of an amount of metal ions (eg iron, vanadium and copper ions) and in the presence of hydrogen peroxide in an amount of 8-100 g per mole of monomer.
Molecular weight of 00 (number average) and narrow molecular weight distribution (M _W :
A maleic acid polymer in the acid form having a _MN ratio of less than 2.5). The polymer thus obtained is used as a water treatment agent. According to the description in the comparative example, maleic acid neutralized to 50 or 23.7% is polymerized in the presence of an initiator system consisting of hydrogen peroxide and iron ions, with a high residual maleic acid residue. A quantity of polymer is produced.

[0005]

The object of the present invention is to have a monoethylenically unsaturated dicarboxylic acid content of 65% by weight or more and a residual monoethylenically unsaturated dicarboxylic acid content of 1.
The aim was to develop a process for the production of homo- and copolymers of monoethylenically unsaturated dicarboxylic acids which makes it possible to obtain such polymers as below 5% by weight.

[0006]

According to the present invention, the above-mentioned problems are solved by the following components: (a) monoethylenically unsaturated C ₄ -C ₈ dicarboxylic acid (b) hydroxy C ₂ -C ₄ alkyl acrylate and / or hydroxy C ₂ -C ₄ alkyl methacrylate (c) other water-soluble monoethylenically unsaturated monomers (a) :( b) :( c) is (100-65) :( 0-3
5): at a weight ratio of (0-35), 7-50 by radical polymerization in a partially neutralized form in an aqueous solution.
K value of (by H. Fikentscher in 1% aqueous solution, pH
In a process for preparing homopolymers and copolymers of monoethylenically unsaturated dicarboxylic acids having a Na salt of the polymer at 7 and 25 ° C., the neutralization rate of the monomer having an acid group during polymerization is 52-70%. Adjust to
At that time, the monomer (a) and the monomer (c) having an acid group
In the case of producing a copolymer from the above, the neutralization rate of the monomer (a) can be up to 85% at the start of the polymerization, and the monomer (c) having this acid group should be used in a non-neutralized form. And a method for producing homo- and copolymers of monoethylenically unsaturated dicarboxylic acid.

Monoethylenically unsaturated C ₄ -C ₈ dicarboxylic acids are mentioned as monomers of group (a). Suitable dicarboxylic acids are, for example, maleic acid, fumaric acid,
Itaconic acid, mesaconic acid, methylenemalonic acid and citraconic acid. Of course, an anhydride of dicarboxylic acid may be used, which is converted to dicarboxylic acid when dissolved in water. Suitable anhydrides of this type are, for example, maleic anhydride, itaconic anhydride and methylenemalonic anhydride. Monomers which can be used advantageously in these groups are maleic acid, fumaric acid and itaconic acid, in particular those which give maleic acid when dissolved in maleic anhydride or water. It The monomers of group (a) can be used alone as homopolymers or mixed with one another as copolymers, and when producing the copolymers, when producing the copolymers, the monomers of groups (b) and / or (c) can be used. ) Monomer to form a copolymer. When a copolymer is prepared, it contains 65% of the monomers of group (a).
% Or more, preferably 80 to 95% by weight, incorporated by polymerization.

Monomers of group (b) include hydroxy-C ₂ -C ₄ alkyl acrylates and / or the corresponding methacrylates. Compounds of this type are, for example, 2-hydroxyethyl acrylate, 2-
Hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate,
4-Hydroxybutyl acrylate, 4-hydroxybutyl methacrylate and a mixture of the abovementioned hydroxyalkyl (meth) acrylates, wherein all the isomers and isomer mixtures of the individually mentioned hydroxyalkyl (meth) acrylates Can be used as the monomer of component (b). From the group of monomers, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate can advantageously be used. The monomers of group (a) are the same as those of group (b)
Together with the monomer of (100-65): (0-35),
Preference is given to copolymerizing in a weight ratio of (99-80) :( 1-20).

Monomers of group (c) are other water-soluble monoethylenically unsaturated monomers capable of copolymerizing with monomers (a) and (b). Examples of monomers of group (c) are C _{3 to} C ₁₀ monocarboxylic acids,
Examples are acrylic acid, methacrylic acid, dimethylacrylic acid, ethylacrylic acid, allylacetic acid and vinylacetic acid. From this group of monomers acrylic acid, methacrylic acid and mixtures thereof can be used to advantage. In addition thereto, a monomer having a sulfo group as the monomer (c), for example, vinyl sulfonic acid, alice sulfonic acid, methallyl sulfonic acid, styrene sulfonic acid, acrylic acid-3-sulfopropyl ester, methacrylic acid-3-sulfopropyl Esters, acrylamidomethylpropanesulfonic acid, and monomers containing phosphonic acid groups, such as vinylphosphonic acid,
Allylphosphonic acid and acrylamidoethylpropanephosphonic acid. Water-soluble monoethylenically unsaturated monomers containing no acid groups can also be used in the copolymerization as monomers of group (c), for example amides such as acrylamide, methacrylamide,
N-alkyl acrylamides having 1 to 18 C atoms in the alkyl group, such as N-dimethyl acrylamide, Nt-butyl acrylamide and N-octyl acrylamide, N-vinyl pyrrolidone, N-vinyl caprolactam, N-vinyl imidazole, 1-vinyl
2-methylimidazole, 1-vinylimidazoline, 1
-Vinyl-2-methylvinylimidazoline, N-vinylformamide, N-vinyl-N-methylformamide,
It is a mixture of N-vinylacetamide, N-vinyl-2-methylacetamide and the above-mentioned monomers. The monomer of group (c) can be copolymerized with the monomer of group (a) alone or together with the monomer of group (b).
The weight ratio (a) :( b) :( c) at the time of copolymerization is (100
-65): (0-35): (0-35). If the monomers of group (c) are used together in the copolymerization, this is preferably 1 per 100 parts by weight of copolymer.
~ 20 parts by weight. From this group of monomers, it is advantageous to use acrylic acid, methacrylic acid and acrylamidomethylpropanesulfonic acid.

For the modification of the copolymers, the monomers of group (d) may be used in combination in amounts of up to 5% by weight, based on all the monomers used in the polymerization. The monomers of group (d) are cross-linking agents such as N, N-methylenebisacrylamide, acrylic acid, methacrylic acid and maleic acid with polyhydric alcohols and polyalkylene glycols, the ester being 2 Have at least one monoethylenically unsaturated double bond,
For example, glycol diacrylate, glycol dimethacrylate, glycerin triacrylate, glycerin trimethacrylate, polyethylene glycol diacrylate derived from polyalkylene glycol having a molecular weight of 96 to about 2000, as well as the corresponding polyethylene glycol dimethyl acrylate of polyethylene glycol up to a molecular weight of 2000, Polyethylene glycol dimaleinate, glycol dimaleinate and polyols esterified more than once with acrylates or methacrylates, such as pentaerythritol and glucose. Other than that, examples of the crosslinking agent include divinylbenzene, divinyldioxane, pentaerythritol diallyl ether, and pentaallyl saccharose. When a cross-linking agent is also used in the copolymerization, the input amount used here is preferably 0.05 to 5% by weight based on all the monomers used in the polymerization.

The monomers are polymerized in the presence of a modifier in order to produce polymers having a particularly low K value. Suitable preparations include, for example, mercapto compounds, such as mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptoacetic acid, mercaptopropionic acid,
Butyl mercaptan and dodecyl mercaptan. In addition, allyl compounds, such as allyl alcohol, hydroxylamine, formic acid, ethylene glycol, propylene glycol, polyethylene glycol and propylene glycol having a molecular weight of up to 6000, and secondary alcohols, such as isopropanol and s-butanol, are also used as preparation agents. Are suitable. If the polymerization is carried out in the presence of a regulator, 0.05 to 20% by weight are used. Of course, it may also be carried out in the presence of a preparation agent and a monomer of group (d), a so-called cross-linking agent.

This monomer undergoes radical polymerization. Suitable as polymerization initiators are all compounds which form radicals under the polymerization conditions, for example azo compounds and peroxides. The so-called redox system also belongs to this. Water-soluble initiators, such as peroxosulfates, such as sodium peroxosulfate, potassium peroxosulfate and ammonium peroxosulfate, and hydrogen peroxide are preferably suitable. It is advantageous to use redox initiators to accelerate the reaction, especially when the polymerization is carried out at relatively low temperatures. Such a system consists of a compound which provides a radical as usually mentioned, for example a peroxide, a peroxosulfate or a peroxocarboxylate, and a compound which exerts a reducing action, for example sodium bisulfite, sodium disulfite, Included are sodium formaldehyde sulfoxylates, sulfur dioxide, ascorbic acid or mixtures of reducing compounds. Heavy metals such as iron, copper, nickel, chromium, manganese and vanadium ions can also be utilized as soluble salts in the form of redox components. This heavy metal ion is 0.1 to 100,
Preference is given to using amounts of 0.1 to 10 ppm. Sometimes it is advantageous to use a reducing agent in combination with heavy metal ions. As long as the reducing agent is present in the catalyst system, this is 0.1 to 10, preferably 0.2 to 5 relative to the monomer.
The amount is% by weight. The polymerization initiator is used in an amount of 0.5 to 20, preferably 2 to 18% by weight, based on the monomers. As long as a homopolymer or a copolymer having a high maleic acid content is produced, a high initiator amount within the above-mentioned range is used, while the production of the copolymer is controlled to 65-65%.
Used to produce copolymers having a polymerized incorporated maleic acid content in the range of about 80 wt.
An initiator in the range of 5-12% by weight is used.

An aqueous solution of the monomer is polymerized. The concentration of the monomers in the aqueous solution is usually 10 to 70, preferably 20 to 6
It is 0% by weight. The polymerization of the monomer is usually 70 to 150.
C., preferably 80 to 130.degree. It is particularly advantageous to polymerize under boiling conditions of the reaction mixture. If the polymerization temperature is above the boiling point of the reaction mixture, work in a correspondingly equipped pressure device. This polymerization can of course also be carried out under reduced pressure. However, the easiest way is to do it at atmospheric pressure. As is usual in polymerization, under the exclusion of oxygen, for example in an inert gas,
For example, polymerize under nitrogen. It is preferable to take care to mix the reactants well during the polymerization. This can be done, for example, in all reactors equipped with stirrers, eg reactors equipped with horseshoe stirrers.

In the case of the present invention, the neutralization rate of the monomer having an acid group is adjusted to 52 to 70% during homopolymerization and copolymerization, so that a partially neutralized copolymer is obtained immediately after the polymerization. Occurs, in which case the monomer containing polymerized incorporated acid groups is 52-70%, preferably 55-65%.
Have been neutralized.

In the production of a copolymer in which the monomer (a) and the comonomer (c) having an acid group are copolymerized, the monomer (c) having an acid group is continuously added in a non-neutralized form, up to 85%. When the neutralized monomer (a) is added, first, the neutralization rate of the monomer (a) that exceeds the range of 52 to 70% can be adjusted. After the feed of the monomer (c) has ended, polymerisation again results in a partially neutralized copolymer having a neutralization rate of 52 to 70% of the incorporated acid groups, preferably 55 to 65%. .. Copolymers consisting of monomers (a) and (b), or copolymers consisting of (a) and acid-free monomers (c) and optionally monomers (d), or monomers (a), (b), acid-free. So long as a copolymer of the monomer (c) and optionally the monomer (d) is copolymerized, preferably the monomers of group (a) are from 10 to 70.
%, In the form of an aqueous solution of 52-70%, preferably 55-65%
It is possible to surely remove the heat of polymerization to the reaction mixture by adding the comonomer and the initiator to the reaction mixture to the extent that the copolymerization proceeds, that is, at the neutralization rate of Add at a rate such that the polymerization reaction can be well controlled.

Monomer (a) and monomer (c) having an acid group and optionally (b) and optionally (d)
Another method of maintaining the neutralization ratio within the above range during copolymerization with
% Of the monomer having acid groups (c), and optionally the remaining comonomers, together with a base, from an aqueous solution charged with the partially neutralized monomer (a). As a result, the monomer (c) having acid groups likewise has a neutralization rate in the range from 52 to 70%, preferably 55 to 65%. However, the monomer (c) having an acid group can also be added in the already partially neutralized form to the partially neutralized, charged aqueous solution of the monomer (a). However, the monomer (c) having an acid group is
Even if the neutralization rate is less than 52%, it can be added to the monomer (a) neutralized by 60% or more. In this case, it is important that the units (c) and (a) with acid groups polymerized and incorporated in the copolymer have a total neutralization rate of 52-70%. However, it can sometimes be advantageous to supply the monomer (c) having acid groups in a partially or completely neutralized form. However, in this case, the charged monomer (a) must be neutralized accordingly.

Alkali metal bases, ammonia and / or amines are used for the neutralization. Preference is given to using sodium hydroxide or potassium hydroxide. Examples of amines that can be used for neutralization include ethanolamine, diethanolamine, triethanolamine,
Morpholine and mixtures thereof are suitable.

In order to produce colorless or slightly colored homopolymers and copolymers from the monomers (a) to (d), the polymerization is preferably carried out by using a water-soluble phosphorus compound in which phosphorus has an oxidation number of 1 to 4; Alkali metal salt or ammonium salt, a compound having a water-soluble —PO (OH) ₂ — group and / or the presence of a water-soluble salt thereof. Preference is given to using phosphorous acid. The phosphorus compounds mentioned here are used in an amount of 0.01 to 5% by weight, based on the monomers used, in order to reduce the coloration of the polymers. The phosphorus compounds listed here are described in EP 0175317 for other polymerization methods.

The process according to the invention gives polymers having a K value of 7 to 50, preferably 8 to 30 (measured at 25 ° C. for an aqueous solution of 1% polymer adjusted to pH 7 with caustic soda solution). The homopolymers and copolymers obtained by the process of the invention have a relatively low content of residual monomers of group (a). The residual monomer amount of maleic acid is, for example, 1.5% or less calculated as a solid. The polymer thus obtained can therefore be fed directly to the intended application or used after complete neutralization. The homopolymers and copolymers can be used, for example, as additives for detergents and dishwashing detergents, respectively in an amount of 0.1 to 15% by weight, based on the total preparation.

The dish detergent is, for example, 5 to 20% by weight of ammonium carbonate or alkali metal carbonate or ammonium sulfate or alkali metal sulfate, 2% by weight or more of alkali metal silicate, and 0.5 to 8 antifoaming surfactant. %, As well as the other main constituents of the polymers obtained by the process according to the invention. The dish detergent may contain up to 94% by weight sodium silicate and up to about 50% by weight ammonium carbonate or alkali metal carbonate. In addition, compounds capable of releasing active chlorine, such as potassium or sodium salts of dichloroisocyanurate, can be included, the active chlorine content of the preparation being up to 3% by weight. In addition, gluconic acid or glucoheptonic acid or its alkali metal salts may still be contained up to 20% by weight. The dishwashing detergent optionally further comprises customary additives such as defoamers, colorants, fragrances, dust binders and already marketed polymers such as 70% by weight of polyacrylates or acrylic acid and 30% by weight of maleic acid. The copolymer can be contained in the usual amounts supplied for this. The above figures are understood to be only a rough reference point for the composition, as the composition of the dishwashing detergent varies significantly.

The homopolymers and copolymers obtained by the process according to the invention can also be used in the washing of fibers. For this, the polymer solution obtained in the polymerization is often dried in conventional driers, for example drum driers, spray driers and spray fluidized bed driers, to powders or granules.

The polymer exhibits a film-blocking action and a pigment stain dispersing action. The polymer can also be used in liquids, as well as in powder detergents and cleaners. This polymer exhibits a better compatibility, especially in liquid detergent preparations, than the copolymers of monomer (a) known from EP 0025551 and monomer (c) having an acid group. ing.

The composition of the detergent preparation may vary significantly. The same applies to the composition of the detergent preparation. Detergent and detergent preparations contain customary surfactants and optionally builders. This description is
The same applies to detergent and detergent preparations on liquids and powders. Examples of compositions of detergent preparations commonly used in Europe, the United States and Japan are, for example:
Chemical and Engn. News, 67, 35 (1989) by table, and Ullmanns Encyklopaed.
ie der technischen Chemie, Verlag Chemie, Weinheim 1
983, 4th edition, pp. 63-160.

The above-mentioned polymers can be used according to the invention in detergents containing up to 45% by weight of phosphate, the polymers having a low phosphate content (for which phosphorus Sodium acid 25% by weight
The following are understood as phosphate content) or are used in phosphate-free detergents as well as in detergents. The polymer can then be added to the detergent preparation in the form of granules, pastes, high-viscosity materials or as a dispersant or as a solution in a solvent. The polymer may be adsorbed on the surface of extenders such as sodium sulphate or builders (zeolites or bentonites), as well as other solid auxiliaries of detergent preparations.

The detergent and detergent preparations are in powder or liquid form. It may be disciplined or of different composition depending on the particular application.

The general household detergents for drum type washing machines which are widely used in Europe usually have an anionic surfactant 5-1.
0% by weight, 1 to 5% by weight of nonionic surfactant, foaming regulator such as 1 to 5% by weight of silicone oil or soap, softener for hard water such as 0 to 40% by weight of soda or pentasodium triphosphate ( Can be partially or completely replaced by the compounds according to the invention), ion exchangers such as 0-30% by weight of zeolite A, 2-7% by weight of sodium silicate as corrosion inhibitor, bleaching agents such as peroxoboric acid. Sodium, sodium peroxocarbonate, organic acid or its salt 10 to 30% by weight, bleach activator such as tetraacetylethylenediamine, pentaacetylglucose, hexaacetylsorbit,
Or 0 to 5% by weight of acyloxybenzene sulphonate, stabilizers such as magnesium silicate or ethylenediamine tetraacetate, anti-graying agents such as carboxymethyl cellulose, methyl- and hydroxyalkyl celluloses, polyglycols grafted with vinyl acetate, oligomers and polymers. Contains terephthalic acid / ethylene glycol / polyethylene glycol ester, enzymes, optical brighteners, perfumes, softeners, colorants and extenders.

In contrast, heavy duty detergents used by the United States of America, Japan and other adjacent countries in tub washing machines are mostly bleach-free and contain a proportion of anionic surfactant. 2 to 3 times higher, this detergent contains more washing alkali, such as soda and sodium silicate (in principle up to 25% by weight), and is mostly free of bleach activators and bleach stabilizers. The weight indication of surfactants and other contents is still enhanced in the case of so-called concentrated detergents which contain no or a small amount of filler. Delicate and patterned detergents, wool detergents and hand-wash detergents all contain mostly no bleaching agents and, in the case of correspondingly high surfactant components, less alkaline components. ..

Detergents for the commercial field, which are able to meet the requirements such as the type of laundry and the type of soiling, are prepared in special proportions for industrial washing (soft water, continuous washing). Therefore, compositions are used in which one component predominates or is completely devoid of other components, which compositions are supplied separately as needed. The component surfactants, builder (Gerueststoff), the alkalis and bleaches of this detergent thus vary widely.

Suitable anionic surfactants for the abovementioned powder detergents are, for example, sodium benzenebenzenesulfonate, fatty alcohol sulphates, fatty alcohol polyglycol ether sulphates. Compounds herein of this type are, for example, C _{8 to} C ₁₂ alkylbenzene sulphonates, C _{12 to} C ₁₆ alkane sulphonates, C
₁₂ -C ₁₆ alkyl sulfosuccinates and sulfated ethoxylated C ₁₂ -C ₁₆ alcohol. Other than that, as anionic surfactant, sulfated fatty acid alcohol amine, α-sulfo fatty acid ester, fatty acid monoglyceride or a reaction product of primary or secondary fatty alcohol or alkylphenol and ethylene oxide 1 to 4 mol is suitable. There is. Further suitable anionic surfactants are fatty acid esters of hydroxycarboxylic acids or aminocarboxylic acids or hydroxysulfonic acids or aminosulfonic acids, or fatty acid amides, such as fatty acid sarcosides, -glycolates, -lactates, -taulides or isothionates. .. The anionic surfactants may be in the form of sodium, potassium and ammonium salts and as soluble salts of organic bases such as mono-, di- or triethanolamine or other substituted amines. A common soap, that is, an alkaline salt of a natural fatty acid also belongs to this anionic surfactant.

Nonionic surfactants such as ethylene oxide 3 to 40, preferably 4 to 2
Addition products of 0 mol with 1 mol of fatty alcohol alkylphenols, fatty acids, fatty amines, fatty acid amides or alkanesulfonamide can be used. The above-mentioned addition product of ethylene oxide may optionally contain additionally polymerized and incorporated up to 90% by weight of propylene oxide with respect to ethylene oxide and propylene oxide incorporated and polymerized. The addition product containing the polymerized incorporation of ethylene oxide and propylene oxide may optionally comprise 60% by weight, based on the total alkylene oxide content.
May be modified by polymerizing and incorporating butylene oxide in amounts up to. Ethylene oxide 5-16
mol and cocos- or tallow alcohol, oleyl alcohol or synthetic alcohols having 8 to 18, preferably 12 to 18 C atoms, and 6 in alkyl groups.
Of particular interest are addition products with mono- or dialkylphenols having ~ 14 C atoms. In addition to this water-soluble nonionic surfactant, especially when used with a water-soluble nonionic or anionic surfactant,
Water-insoluble or not completely water-soluble polyglycol ethers having 1 to 4 ethylene glycol ether groups in one molecule are important.

Further, as a nonionic surfactant, 2
Having 0 to 250 ethylene glycol ether groups,
And the use of addition products of ethylene oxide with propylene glycol ether groups of 10 to 100 propylene glycol ethers, alkylenediamino polypropylene glycols having 1 to 10 C atoms in the alkyl chain and alkyl polypropylene glycols. Of which the polypropylene glycol ether chain functions as a hydrophobic group.

Nonionic surfactants of the amino oxide or sulfoxide type can also be used.

The foaming capacity of this surfactant can be improved or reduced by the combination of suitable surfactant types. Similarly, the reduction can be achieved by adding non-surfactant organic substances.

Other mixing components of the detergent may be unsaturated fatty alcohol-based monomeric, oligomeric and polymeric phosphonates, ether sulphonates such as oleyl alcohol ethoxylate butyl ethers and their alkali salts. Such materials, for example, the _{formula: RO (CH 2 CH 2 O} ) n-C 4 H 8 -
SO ₃ Na (wherein, n represents 5 to 40, R represents oleyl) can be characterized by those represented by the.

The polymers described above can also be used as additives in liquid detergents. The liquid detergent is contained as a mixed component of a liquid or solid surfactant which is soluble or at least dispersible in the detergent preparation.
In this regard, surfactants include products that can also be used in powder detergents and can be used in liquid polyalkylene oxides or polyalkoxylated compounds. If this polymer cannot be mixed directly with other customary constituents of liquid detergents, small amounts of solubilizers, such as water, or water-miscible organic solvents, such as isopropanol, methanol, ethanol, glycols or ethylene glycol. It can be prepared using glycol or the corresponding propylene glycol, a homogenous mixture. The amount of surfactant in the liquid detergent is from 4 to 50% by weight, based on all the preparations, since in the case of liquid detergents, depending on the local market situation or application purpose, The ratio of varies over a wide range.

This liquid detergent contains 10 to 60% by weight of water,
It can preferably be contained in an amount of 20 to 50% by weight.
However, it may also be water-free.

The water-free liquid detergents may contain peroxy compounds in suspended or dispersed form for bleaching. Peroxy compounds include, for example, sodium peroxoborate, peroxocarboxylic acids and partially peroxo-containing polymers. In addition, the liquid detergent can optionally contain a hydrotrope. For this,
It is understood to be compounds such as 2-propanediol, cumol sulfonate and toluene sulfonate. When compounds of this type are used for modifying liquid detergents, their amounts are 2-5% by weight, based on the total weight of the liquid detergents. In many cases, it is also advantageous to add complexing agents for the modification of powder and liquid detergents. Complexing agents are, for example, ethylenediaminetetraacetic acid, nitrotriacetate and isoserinediacetic acid, and phosphonates such as aminotrimethylenephosphonic acid, hydroxyethanediphosphonic acid, ethylenediaminetetraethylenephosphonic acid and salts thereof. This complexing agent is used in an amount of 0 to 10% by weight, based on the detergent. In addition, the detergent may contain citrate, di- or triethanolamine, opacifying agents, optical brighteners, enzymes, perfume oils and colorants. This material is used in amounts of up to 5% by weight when used for the modification of liquid detergents. The detergent is advantageously phosphate-free. However, it may also contain phosphates, such as pentasodium triphosphate and / or tripotassium pyrophosphate. If phosphates are used, the proportion of phosphate with respect to the total detergent preparation is up to 45% by weight, preferably up to 25% by weight.

This polymer is combined with other known detergent additives (eg graying inhibitors, clay dispersants and substances which enhance the primary detersive action, color transfer inhibitors, bleach activators) in powder and liquid detergents ( Interactions can be induced in phosphate-containing and phosphate-free), with the effect of not only graying inhibitors but also other detergent additives being enhanced.

The K value is H. Fikentscher, Cellulosechemi.
e, 13 volumes, 58-64 and 71-74 (1932)
It was measured by. In this case, K = k · 10 ³ . This measurement was carried out at a pH value of 7 at 25 ° C. on a 1% aqueous solution of the sodium salt of the polymer. The residual content of the monomeric maleic acid in the polymer is measured by the polarographic method. Percentage representations for maleic acid remaining in the polymer are calculated on solids. This percentage display is% by weight.

[0040]

【Example】

Examples 1 to 4 and Comparative Example 1 In a heatable reactor equipped with stirrer, reflux condenser, thermometer, feed and nitrogen inlet, 300 g of water, 380.17 g of maleic anhydride, 50% aqueous sub-substance. 3 g of phosphoric acid,
20 ml of an aqueous solution of ammonium iron sulfate II 0.035%
And charging with the amount of sodium hydroxide listed in Table 1,
Heat to boiling under nitrogen. To the continuously stirring boiling solution was added during 5 hours a solution of 50 g of hydroxypropyl acrylate in 80 g of water and separately over the course of 6 hours 226 g of 30% hydrogen peroxide. This polymerization was carried out under boiling of the reaction mixture. After the addition of hydrogen peroxide was complete, the reaction mixtures were each heated and boiled for a further 2 hours. Subsequently, it was neutralized to a pH value of 6.8 by adding 50% of aqueous caustic soda solution in the amount indicated in Table 1. Table 1 lists the solids content of the polymer solution, the K value of the polymer, and the content of unpolymerized maleic acid in the copolymer.

[0041]

[Table 1]

Examples 5-10 and Comparative Examples 2-4 Into the reactor described in Example 1, 300 g of water, 338 g of maleic anhydride and the amount of sodium hydroxide described in Table 2, respectively, were charged and heated to boiling. Let To this boiling mixture was added a solution of 100 g of acrylic acid in 110 g of water over a period of 5 hours, apart from this, a solution of 20 g of sodium peroxosulfate in 70 g of water and water 2 during 6 hours.
A solution of 66.6 g of 30% hydrogen peroxide in 3.34 g was added uniformly and the polymerization was carried out under boiling of the reaction mixture.
After adding the initiator, the reaction mixture was heated to boiling for a further 2 hours. A clear yellow polymer solution was obtained, the solids content of which is given in Table 2. Similarly, Table 2 shows the K value of the polymer and the residual amount of maleic acid.

[0043]

[Table 2]

Example 11 In the reactor described in Example 1, 270 g of water, 401.3 g of maleic anhydride and 213.42 g of sodium hydroxide.
Was charged and heated to boiling. Immediately after boiling started, 5
During the time, a solution of 25 g of acrylic acid in 80 g of water is fed, during a period of 6 hours a solution of 50 g of sodium peroxosulfate in 120 g of water is fed, and separately, 100 g of 50% hydrogen peroxide is fed. The reaction mixture was then polymerized at the boiling point. After addition of the initiator, the reaction mixture was heated to boiling for a further 2 hours and subsequently neutralized by adding 100 g of 50% aqueous sodium hydroxide solution. The neutralization rate of this charge was about 65%. After the addition of acrylic acid was complete, the combined neutralization rate of carboxylic acid groups in the copolymer was 62.5%. The resulting clear brown solution had a solids content of 53.4%.
This copolymer had a K value of 12.1 and contained 0.12% of the monomeric maleic acid.

Example 12 In the reactor described in Example 1, 300 g of water, 388 g of maleic anhydride and 7 ml of a 0.1% aqueous solution of ammonium iron sulfate II and 193.15 g of sodium hydroxide were mixed and heated to boiling. .. Immediately after the boiling started, a solution of 50 g of acrylic acid, 95.35 g of a 58% aqueous solution of sodium acrylamidomethylpropanesulfonic acid and 30.6 g of water were supplied for 5 hours, and after boiling started, A solution of 40 g of sodium peroxosulfate in 120 g of water and 30% hydrogen peroxide 13 over 6 hours
3.33 g was fed. After the initiator was added, the reaction mixture was heated to boiling for another hour and subsequently neutralized to pH 7.0 with 50% aqueous sodium hydroxide solution. The slightly cloudy brown solution thus obtained had a solids content of 50.8%. This copolymer had a K value of 13.3 and contained 1.06% of the monomeric maleic acid.

Example 13 Application test of polymers as dish detergent additives The following powdered dish detergent formulations were tested in the examples according to the invention and in the comparative examples.

Sodium sulfate 32 parts Sodium metasilicate (water-free) 55 parts Sodium carbonate (water-free) 5 parts Ethylene oxide 2 mol and propylene oxide 4
Addition product of mol with 1 mol of C ₁₃ / C ₁₅ fatty alcohol 3 parts polymer 5 parts This preparation was obtained by mixing the abovementioned products.
The products listed in the following table were tested as polymers. To test the formulation here, 2 g of formulation per 1 l of drinking water were used (18 ° German hardness) and the aqueous solution of formulation was heated. The utensil was then dipped and the solution was stirred for 5 minutes using a porcelain stirrer and the utensil was left in the aqueous dishwashing liquid at 80 ° C for a further 5 minutes. Then, this eating utensil was dried at 23 degreeC, without rinsing, and the deposit formation was evaluated using the evaluation scale which calculates the score of 1-5. A score of 1 represents the worst result, i.e. a white coating is clearly visible, while a score of 5 represents a very good result, i.e. no coating. The polymers used in each of the preparations here as well as the results are shown in Table 3.

[0048]

[Table 3]

Example 14 Application test of polymers as detergent additives For comparison, a commercial copolymer of 70% by weight acrylic acid and 30% by weight maleic acid was used in the form of the sodium salt having a K value of 60. This copolymer is hereinafter referred to as Comparative Polymer 1.

The film-inhibiting action and the stain-dispersing action (clay dispersion test) were measured.

Film-Inhibiting Action In order to test the film-inhibiting action of the abovementioned polymers, the polymers were intimately mixed in phosphoric acid-free powder detergents. A cotton fabric test fabric was washed with this detergent preparation. The number of washing cycles was 10. The fabric was ironed and dried after each cycle. After washing this number of times, each test fabric was ashed and the ash weight of the fabric was measured. The more effective the polymer contained in the detergent, the lower the ash weight of the test fabric.

Test conditions for film measurement Instrument: Launder-O-Meter Fa. Atlas, Chicago Number of washing cycles: 10 Washing liquid: 250 g, water used having a hardness of 4 mmol per liter. .. (Molar ratio calcium to magnesium = 3: 1) Washing time: 30 minutes at 60 ° C (including heating time) Detergent dose 8g / l Cotton fabric 20g Detergent (without phosphate) Dodecylbenzene sulfonate (50%) 12 C ₃ / C ₁₅ with .5% 7 ethylene oxide units - oxo alcohol polyglycol ether 4.7% soap 2.8% zeolite a 25% sodium carbonate 12% Na-disilicate 4% Mg- disilicates 1% peroxoborate Sodium acid 20% Copolymer according to example or comparative example 5% (calculated at 100%) Na-carboxymethylcellulose 0.6% Sodium sulphate up to 100% remaining Effect on polymer film formation Copolymer additive to detergent preparation Ash weight (%) ───────────────── ─────────────── 1.29 Comparative polymer 1 0.57 Polymer according to Example 8 0.59 Polymer according to Example 9 0.49 Clay dispersion Particle dirt on textile surface The removal is performed by adding a polyelectrolyte. Stabilization of the dispersion after separating the particles from the fiber surface is an important issue for this polyelectrolyte. The stabilizing action of the anionic dispersant is caused by the adsorption of dispersant molecules on the solid surface, resulting in an increase in the surface charge and an increase in repulsive energy. Other influence values for the stability of the dispersant are also electrostatic effects, temperature, pH value and electrolyte concentration.

The clay dispersion test (CD test) described below can be used to easily determine the dispersibility of different polyelectrolytes.

CD Test Finely ground China clay (China-Clay SPS 151) is used as a model for particulate dirt. Clay 1
g was vigorously dispersed in a stand cylinder (100 ml) for 10 minutes while adding 1 ml of a 10% sodium salt solution of polyelectrolyte in 98 ml of water. Immediately after stirring, 2.5 ml sample from the center of the stand cylinder
Was taken, diluted with water to 25 ml, and the haze of the dispersion was measured using a nephelometer. After leaving the dispersion for 30 minutes or 60 minutes, a fresh sample was taken and the haze was measured as described above. The cloudiness of the dispersion is NTU (nephelometric
turbidity units). The more the dispersion does not settle on storage, the higher the measured haze and the more stable the dispersion.

As the second physical measurement value, the dispersion constant τ showing the temporal behavior of the deposition process is measured. This deposition process is almost monoexponential time law (monoexponentielles Zeitgeset
Since it can be represented by z), cloudiness is a time point t = 0.
1 / e times that of the starting state in.

The higher the value of τ, the slower the precipitation of the dispersion.

Clay-Dispersion Test Material Tested Haze in NTU after Storage Dispersion Constant Immediately 30 minutes 60 minutes τ ───────────────────────── No polymer 600 37 33 33 41.4 Comparative Polymer 1 640 470 380 97.2 Polymer according to Example 8 660 550 500 234.9 Polymer according to Example 600 600 540 500 261.0 Inventive It is speculated that the copolymers are superior in having a lower maleic acid content than commercial copolymers. The copolymers according to the invention were clearly more effective in the extent of the primary cleaning action in the clay dispersion test, in the case of some comparable film-inhibiting action.

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[Procedure amendment]

[Submission date] May 2, 1991

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 3

[Correction method] Change

[Correction content]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0015

[Correction method] Change

[Correction content]

In the production of a copolymer in which the monomer (a) and the comonomer (c) having an acid group are copolymerized, the monomer (c) having an acid group is continuously added in a non-neutralized form, up to 85%. When the neutralized monomer (a) is added, first, the neutralization rate of the monomer (a) that exceeds the range of 52 to 70% can be adjusted. After the feed of the monomer (c) has ended, polymerisation again results in a partially neutralized copolymer having a neutralization rate of 52 to 70% of the incorporated acid groups, preferably 55 to 65%. .. Copolymers consisting of monomers (a) and (b), or copolymers of (a) and acid-free monomers (c) and optionally monomers (d), or monomers (a), (b), acid-free. As long as a copolymer of the monomer (c) of (1) and optionally the monomer (d) is copolymerized, the monomers of group (a) are preferably from 10 to 70.
%, In the form of an aqueous solution of 52-70%, preferably 55-65%
At a neutralization rate of, and a comonomer and, subsequently, an initiator are added to the reaction mixture as the copolymerization proceeds .
The trimer comonomer and initiator are added to the reaction mixture at a rate such that the heat of polymerization can be reliably removed and the polymerization reaction is well controllable.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hans-Jürgen Laubenheimer Germany Ketsch Benz Strasse 6 (72) Inventor Alexander Kut Germany Eppelsheim am Hellbrunn 57 (72) Inventor Richard Bauer Germany Federal Republic Mutterstadt Nerkenstraße 1 (72) Inventor Hans-Werner Neumann Federal Republic of Germany Reilingen Kantstraße 3 (72) Inventor Dieter Steckt Germany Ludwigshafen Königstraße 4

Claims (5)

[Claims] 1. The following components: (a) monoethylenically unsaturated C ₄ -C ₈ dicarboxylic acid (b) hydroxy C ₂ -C ₄ alkyl acrylate and / or hydroxy C ₂ -C ₄ alkyl methacrylate (c) other The water-soluble monoethylenically unsaturated monomer of (a) :( b) :( c) is (100-65) :( 0-3
5): at a weight ratio of (0-35), 7-50 by radical polymerization in a partially neutralized form in an aqueous solution.
In the method for producing homo- and copolymers of monoethylenically unsaturated dicarboxylic acid having a K value of, the neutralization rate of the monomer having an acid group is adjusted to 52 to 70% during the polymerization, and the monomer (a And a monomer (c) having an acid group, the neutralization rate of the monomer (a) can be up to 85% at the start of the polymerization. A method for producing homo- and copolymers of monoethylenically unsaturated dicarboxylic acid, which is used in a non-neutralized form. 2. The weight ratio of (a) :( b) is (99-6).
5): The method according to claim 1, wherein the copolymer is composed of the monomers (a) and (b), wherein (1 to 35) and the neutralization rate of the monomer (a) is 55 to 65%. 3. The weight ratio of (a) :( c) is (99-6).
5): (1-35), in which the monomer (a) is charged into the polymerization reactor, which is neutralized with an alkali metal base, ammonia or amine to a neutralization rate of 85% and subsequently started The process according to claim 1, wherein a copolymer of monomers (a) and (c) is added in which the agent and the monomer (c) having an acid group in unneutralized form are added so that the polymerization proceeds. 4. The weight ratio of (a) :( b) :( c) is (9).
9-65): (1-35): (1-35), and is composed of monomers (a), (b) and (c) in which the total neutralization rate of the monomer having an acid group is 55-65%. The method of claim 1 for producing a copolymer. 5. Detergents and dishwashing detergents which contain the homopolymers and copolymers obtained by the process according to any one of claims 1 to 4 in an amount of 0.1 to 15% by weight, based on the total preparation. Additive.